促进和调整异质和同质双金属锌配合物的电化学还原**,ChemElectroChem

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促进和调整异质和同质双金属锌配合物的电化学还原**
ChemElectroChem ( IF 3.5 ) Pub Date : 2021-05-12 , DOI: 10.1002/celc.202100358
Shaun Kelsey ₁ , Amit Kumar ₁ , Allen Oliver ₂ , Victor Day ₁ , James Blakemore ₃

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由于这些物质有用的氧化还原和反应特性，含有多种金属的化合物引起了极大的兴趣。在这里，一系列大环配合物的电化学性质具有锌（II）中心与异双金属（Na ⁺，Ca ²⁺，Nd ³⁺，Y ³⁺）基序或同双金属（锌²⁺) 主题已被调查。新的配合物是通过发散策略制备的，分离出来的，并用单晶 X 射线衍射 (XRD) 分析对其进行结构表征。XRD 结果表明配合物的结构受掺入的次级金属离子的特性调节。循环伏安法数据表明，在双金属配合物中促进了以配体为中心的还原，并且成对的金属离子协同影响配合物的氧化还原性能。与我们小组和其他人之前的工作类似，含有更强路易斯酸的双金属配合物经历了更显着的还原电位变化；然而，与先前对含有氧化还原活性金属的配合物的研究相比，与单价（和更弱酸性）钠相比，当加入二价或三价路易斯酸时，这里研究的锌 (II) 配合物显示出更快的电子转移（根据较低的重组能，λ 判断）。这些数据中的量化趋势提供了有助于区分金属与配体中心还原双金属配合物的见解。

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Promotion and Tuning of the Electrochemical Reduction of Hetero- and Homobimetallic Zinc Complexes**

Compounds containing multiple metals attract significant interest due to the useful redox and reactivity properties of such species. Here, the electrochemical properties of a family of macrocyclic complexes that feature a zinc(II) center paired with a secondary redox-inactive metal cation in heterobimetallic (Na⁺, Ca²⁺, Nd³⁺, Y³⁺) motifs or homobimetallic (Zn²⁺) motifs have been investigated. The new complexes were prepared via a divergent strategy, isolated, and structurally characterized with single-crystal X-ray diffraction (XRD) analysis. XRD results show that the structures of the complexes are modulated by the identity of the incorporated secondary metal ions. Cyclic voltammetry data reveal that ligand-centered reduction is promoted in the bimetallic complexes and that the paired metal ions synergistically influence the redox properties of the complexes. Similar to prior work from our group and others, the bimetallic complexes containing stronger Lewis acids undergo more significant reduction potential shifts; contrasting with prior work on complexes containing redox-active metals, however, the zinc(II) complexes studied here display faster electron transfer (as judged by lower reorganization energies, λ) when incorporating di- or tri-valent Lewis acids in contrast to monovalent (and more weakly acidic) sodium. The quantified trends in these data offer insights that could help distinguish metal- versus ligand-centered reduction of bimetallic complexes.

更新日期：2021-05-12

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